US20160027561A1 - Ceramic electronic component - Google Patents

Ceramic electronic component Download PDF

Info

Publication number
US20160027561A1
US20160027561A1 US14/805,546 US201514805546A US2016027561A1 US 20160027561 A1 US20160027561 A1 US 20160027561A1 US 201514805546 A US201514805546 A US 201514805546A US 2016027561 A1 US2016027561 A1 US 2016027561A1
Authority
US
United States
Prior art keywords
ceramic
resin
electronic component
coating film
ceramic element
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US14/805,546
Other versions
US9959975B2 (en
Inventor
Mitsunori Inoue
Yoshihito Okutomi
Tomohiko Mori
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Murata Manufacturing Co Ltd
Original Assignee
Murata Manufacturing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Murata Manufacturing Co Ltd filed Critical Murata Manufacturing Co Ltd
Assigned to MURATA MANUFACTURING CO., LTD. reassignment MURATA MANUFACTURING CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INOUE, Mitsunori, MORI, TOMOHIKO, OKUTOMI, YOSHIHITO
Publication of US20160027561A1 publication Critical patent/US20160027561A1/en
Application granted granted Critical
Publication of US9959975B2 publication Critical patent/US9959975B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/10Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00Fixed capacitors; Processes of their manufacture
    • H01G4/30Stacked capacitors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C1/00Details
    • H01C1/01Mounting; Supporting
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C1/00Details
    • H01C1/02Housing; Enclosing; Embedding; Filling the housing or enclosure
    • H01C1/028Housing; Enclosing; Embedding; Filling the housing or enclosure the resistive element being embedded in insulation with outer enclosing sheath
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C1/00Details
    • H01C1/14Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/008Thermistors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H01C7/021Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient formed as one or more layers or coatings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/04Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
    • H01C7/041Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient formed as one or more layers or coatings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/10Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
    • H01C7/1006Thick film varistors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/18Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material comprising a plurality of layers stacked between terminals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00Fixed capacitors; Processes of their manufacture
    • H01G4/002Details
    • H01G4/018Dielectrics
    • H01G4/06Solid dielectrics
    • H01G4/08Inorganic dielectrics
    • H01G4/12Ceramic dielectrics
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00Fixed capacitors; Processes of their manufacture
    • H01G4/002Details
    • H01G4/018Dielectrics
    • H01G4/06Solid dielectrics
    • H01G4/08Inorganic dielectrics
    • H01G4/12Ceramic dielectrics
    • H01G4/1209Ceramic dielectrics characterised by the ceramic dielectric material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00Fixed capacitors; Processes of their manufacture
    • H01G4/002Details
    • H01G4/224Housing; Encapsulation

Definitions

  • the present invention relates to a ceramic electronic component.
  • the ceramics used in electronic components are likely to be chemically eroded by acids or alkalis dues to changes in the ceramic material required by the sophisticated functions of the electronic components.
  • Coating the ceramic element surfaces of the electronic components can reduce the influence of chemical erosion on the ceramic elements, such as that caused by a plating solution during plating or a used in mounting. Further, coating the ceramic element surfaces can, in the case of plating, suppress the growth by plating onto the ceramic element surfaces, and thereby reduce defective conductivity of the electronic component.
  • coating the ceramic element surfaces can prevent ingress of moisture, plating solutions, flux, etc. into the electronic components, and prevent reliability degradation, or electrical property degradation due to deposition by plating onto internal electrodes.
  • the resin coating film needs to have a certain level of thickness, and the surface of the resin coating film may project from the surfaces of wrapping parts of the external electrodes, which are formed on side surfaces of the electronic component.
  • an object of the present invention is to provide a ceramic electronic component where a coating film that has favorable chemical erosion resistance can be inexpensively formed, and defective mounting such as a tombstone phenomenon is unlikely to be caused.
  • the present invention provides a ceramic electronic component including a ceramic element, a coating film provided on a surface of the ceramic element, and an external electrode provided on an end of the ceramic element.
  • the coating film includes a resin, and a cationic element among the constituent elements of the ceramic element.
  • the surface of the coating film is recessed from the surface of a wrapping part of the external electrode, which is formed on a side surface of the ceramic element.
  • the cationic element eluted from the ceramic element is deposited and contained in the coating film.
  • the constituent elements of the ceramic element include at least one of Ba, Ti, Ca, Zr, Fe, Ni, Cu, Zn, Mn, Co, Al, and Si.
  • a plated film may be provided on the external electrode.
  • the coating film includes a resin and at least one kind of cationic elements among the constituent elements of the ceramic element, and the coating film can be selectively formed only on the surface of the ceramic element of the electronic component.
  • the coating film is recessed from the wrapping parts of the external electrodes, and defective mounting such as a tombstone phenomenon is thus unlikely to be caused.
  • the wrapping part of the external electrode formed on the side surface of the ceramic element is preferably brought into contact with the surface of the ceramic element. Then, the wrapping parts of the external electrodes are firmly jointed to the surface of the ceramic element.
  • the ceramic electronic component according to a further aspect of the present invention preferably has a coating film provided in recesses formed at the surface of the ceramic element. Then, the thickness of the coating film on the surface of the ceramic element is reduced in appearance just by the depth dimensions of the recesses, and thus, even when the thickness of the coating film is increased in order to enhance the chemical erosion resistance, the surface of the coating film is recessed from the wrapping parts of the external electrodes, and defective mounting such as a tombstone phenomenon is thus unlikely to be caused.
  • the resin preferably has a thermal decomposition temperature of 240° C. or higher.
  • the resin preferably includes at least one of an epoxy resin, a polyimide resin, a silicone resin, a polyamideimide resin, a polyetheretherketone resin, and a fluorine-containing resin.
  • the ceramic electronic component has high heat resistance.
  • the coating film is preferably cross-linked by heating.
  • the coating film can be formed in a short period of time.
  • the coating film can be selectively formed only on the surface of the ceramic element, and the ceramic electronic component can be obtained whose manufacturing cost is inexpensive.
  • the coating film is recessed from the wrapping parts of the external electrodes, and the ceramic electronic component can be thus obtained which is unlikely to cause defective mounting such as a tombstone phenomenon.
  • FIG. 1 is a cross-sectional view illustrating an embodiment of a ceramic electronic component according to the present invention
  • FIG. 2 is a flowchart showing an example of a method for manufacturing the ceramic electronic component shown in FIG. 1 ;
  • FIG. 3 is a cross-sectional view illustrating a modification example of a ceramic electronic component according to the present invention.
  • a ceramic electronic component according to the present invention will be described with reference to a varistor as an example.
  • FIG. 1 is a cross-sectional view illustrating a varistor 10 that is a ceramic electronic component according to an aspect of the present invention.
  • the varistor 10 includes a substantially cuboidal ceramic element 1 , external electrodes 6 a and 6 b formed on right and left ends of the ceramic element 1 , and a coating film 8 formed so as to cover four side surfaces of the ceramic element 1 .
  • the ceramic element 1 is a laminated body obtained by stacking a plurality of ceramic layers 2 and multiple pairs of internal electrodes 4 a and 4 b opposed to each other with the ceramic layers 2 interposed therebetween.
  • the ceramic layers 2 are composed of a ceramic material in which Bi 2 O 3 is present as a second phase at grain boundaries of a sintered body of ZnO crystal grains with Mn, Co, Sn, or Cr therein as a solid solution.
  • the internal electrodes 4 a have ends extended to the left end surface of the ceramic body 1 , and electrically connected to the external electrode 6 a .
  • the internal electrodes 4 b have ends extended to the right end surface of the ceramic body 1 , and electrically connected to the external electrode 6 b .
  • a varistor function is achieved at sites with the internal electrodes 4 a and 4 b opposed.
  • the internal electrodes 4 a and 4 b are composed of Ag, Cu, Ni, Pd, or an alloy of these metals.
  • the external electrodes 6 a and 6 b respectively have wrapping parts 12 a and 12 b formed to extend on the four side surfaces of the ceramic element 1 .
  • the wrapping parts 12 a and 12 b are formed directly on the surface of the ceramic element 1 .
  • the wrapping parts 12 a and 12 b are firmly joined to the surface of the ceramic element 1 .
  • Plated films 7 a and 7 b are formed on the surfaces of the external electrodes 6 a and 6 b .
  • the plated films 7 a and 7 b protect the external electrodes 6 a and 6 b , and make solderability of the external electrodes 6 a and 6 b favorable.
  • a coating film 8 is formed on parts of the surface of the ceramic element 1 other than regions on which the external electrodes 6 a and 6 b are formed.
  • the coating film 8 is provided in recesses 14 formed by etching the surface of the ceramic element 1 excluding the regions for the external electrodes 6 a and 6 b .
  • the coating film 8 provided in contact with the surfaces of the recesses 14 roughened by etching is firmly joined to the surfaces of the recesses 14 due to the anchor effect.
  • the coating film 8 includes a resin, and cationic elements among the constituent elements of the ceramic element 1 .
  • the cationic elements among the constituent elements of the ceramic element 1 which are contained in the coating film 8 , are deposited by partial elution from the ceramic layers 2 of the ceramic element 1 . More specifically, the cationic elements among the constituent elements of the ceramic element 1 include Zn, Bi, Mn, Co, Sn, Cr, etc. deposited respectively by elution from ZnO, Bi 2 O 3 , MnO, Co 2 O 2 , SnO 2 , Cr 2 O 3 , etc. in the ceramic layers 2 .
  • the resin included in the coating film 8 is a polyvinylidene chloride resin, an acrylic resin, an epoxy resin, a polyimide resin, a silicone resin, a polyamideimide resin, a polyetheretherketone resin, a fluorine-containing resin, or the like.
  • the varistor 10 typically undergoes a mounting step with soldering, and the coating film 8 preferably has high heat resistance (240° C. or higher). Accordingly, a resin is preferred which has a thermal decomposition temperature of 240° C. or higher.
  • the coating film 8 includes a resin and cationic elements among the constituent elements of the ceramic element 1 , and the coating film 8 can be selectively formed only on the surface of the ceramic element of the varistor 10 . Accordingly, the varistor 10 can be obtained whose manufacturing cost is inexpensive.
  • the thickness of the coating film 8 on the surface of the ceramic element 1 is reduced in appearance just by the depth dimensions of the recesses 14 , and thus, even when the thickness of the coating film 8 is increased in order to enhance the chemical erosion resistance, the surface of the coating film 8 can be recessed from the surfaces of the wrapping parts 12 a and 12 b of the external electrodes 6 a and 6 b , and defective mounting such as a tombstone phenomenon is thus unlikely to be caused.
  • FIG. 2 is a flowchart showing an example of a method for manufacturing the varistor 10 .
  • a step S 1 an organic binder, a dispersant, a plasticizer, etc. are added to a ceramic material in which Bi 2 O 3 is present as a second phase at grain boundaries of a sintered body of ZnO crystal grains with Mn, Co, Sn, or Cr therein as a solid solution, thereby preparing slurry for sheet forming.
  • a step S 2 the slurry for sheet forming is formed into sheets by a doctor blade method to provide rectangular ceramic green sheets.
  • an internal electrode paste containing Ag is applied onto the ceramic green sheets by a screen printing method to form electrode paste films which are to be the internal electrodes 4 a and 4 b.
  • a step S 4 the multiple ceramic green sheets with the electrode paste films formed are stacked so as to alternate directions in which ends of the electrode paste films are extended, and subjected to pressure bonding.
  • This laminated ceramic green sheet is cut into a size for individual ceramic elements 1 to provide a plurality of unfired ceramic elements 1 .
  • the unfired ceramic elements 1 are subjected to binder removal treatment at a temperature of 400° C. to 500° C. Thereafter, the unfired ceramic elements 1 are subjected to firing for 2 hours at a temperature of 900° C. to 1000° C. to provide sintered ceramic elements 1 .
  • the ceramic green sheets and the electrode paste films are subjected to co-firing, and the ceramic green sheets serve as the ceramic layers 2 , whereas the electrode paste films serve as the internal electrodes 4 a and 4 b.
  • an external electrode paste (AgPd alloy paste) is applied to both ends of the sintered ceramic elements 1 . Thereafter, on the sintered ceramic elements 1 , the external electrode paste is heated at a temperature of 900° C. to form the external electrodes 6 a and 6 b electrically connected respectively to the internal electrodes 4 a and 4 b.
  • a step S 7 the ceramic elements 1 are immersed in an etching solution to etch the surfaces of the ceramic elements 1 excluding the regions for the external electrodes 6 a and 6 b , thereby forming the recesses 14 .
  • a solution that dissolves the ceramic elements 1 but does not dissolve the external electrodes 6 a and 6 b .
  • a solution which contains an inorganic acid such as a sulfuric acid, a hydrochloric acid, a hydrofluoric acid, and a phosphoric acid.
  • a resin-containing solution is provided by an immersion method, or applied by spin coating.
  • the resin-containing solution has the function of finely etching the surfaces of the ceramic elements 1 to ionize the constituent elements of the ceramic elements 1 , and includes a resin component dissolved or dispersed in an aqueous solvent.
  • the resin-containing solution includes a neutralizer for dissolution or dispersion of the resin component, and if necessary, a surfactant for reaction with cationic elements among the dissolved constituent elements of the ceramic elements. It is to be noted that after providing the resin-containing solution, the ceramic elements 1 are washed with a polar solvent such as pure water, if necessary.
  • the resin-containing solution finely etches (dissolves) the surfaces of the ceramic elements 1 to ionize the constituent elements of the ceramic elements 1 .
  • the etching (dissolving) reaction can be developed just with the constituents of the resin-containing solution without adding any etching promoting constituent such as halogen, because the main constituent is ZnO in the case of the varistor 10 . More specifically, the etching (dissolving) reaction proceeds when the pH of the resin-containing solution is set in a pH range (pH ⁇ 5, pH>11) in which Zn is present stably as ions.
  • the resin component dissolved (dispersed) in the resin-containing solution reacts with cationic elements among the ionized constituent elements of the ceramic elements 1 to neutralize the charge of the resin component.
  • the resin component settles out along with cationic elements among the constituent elements of the ceramic elements 1 , and selectively deposits only on the surface of the ceramic element. Accordingly, in the deposited resin component, at least one kind of cationic elements, which are defined as ionized constituent elements of the ceramic elements, are incorporated.
  • the resin component is not deposited on the external electrodes 6 a and 6 b .
  • the resin component may slightly extend on the surfaces of the external electrodes 6 a and 6 b . This is believed to be the resin component deposited on the surface of the ceramic element, which slightly extends to the external electrodes 6 a and 6 b , rather than the deposition reaction proceeding at the surfaces of the external electrodes 6 a and 6 b.
  • the resin included in the resin-containing solution is a polyvinylidene chloride resin, an acrylic resin, an epoxy resin, a polyimide resin, a silicone resin, a polyamideimide resin, a polyetheretherketone resin, a fluorine-containing resin, or the like, but basically, it does not matter what kind as long as the resin is deposited by the present treatment.
  • the heating treatment is intended to accelerate a cross-linking reaction between the resin components in the resin-containing solution deposited, and the heating condition varies depending on the type of the resin component. In general, the cross-linking reaction is likely to proceed under high temperature. However, the excessively increased temperature increases the decomposition reaction of the resin component. Accordingly, it is preferable to set optimum temperature and time in accordance with the resin component.
  • the plated films 7 a and 7 b are formed on the external electrodes 6 a and 6 b by an electrolytic or electroless plating method.
  • the plated films 7 a and 7 b adopt, for example, a double structure composed of a Ni plated film as a lower layer and an Sn plated film as an upper layer.
  • the coating film 8 can be selectively formed only on the surface of the ceramic element. Accordingly, the varistor 10 whose manufacturing cost is inexpensive can be manufactured with favorable mass productivity.
  • the method can be also adapted to the varistor 10 including the external electrodes 6 a and 6 b which have a complex shape or microstructure, because the coating film 8 is formed by chemical action.
  • FIG. 3 is a cross-sectional view illustrating a modification example of the varistor 10 .
  • a varistor 10 A has the same structure as the varistor 10 shown in FIG. 1 , and detailed description thereof will be thus omitted.
  • a coating film 18 is formed on the surface of the ceramic element 1 excluding the regions for external electrodes 6 a and 6 b .
  • the coating film 18 including a resin, and cationic elements among the constituent elements of the ceramic element 1 is selectively formed only on the surface of the ceramic element 1 of the varistor 10 A.
  • the coating film 18 includes a resin, and cationic elements among the constituent elements of the ceramic element 1 .
  • the cationic elements among the constituent elements of the ceramic element 1 which are contained in the coating film 18 , are deposited by partial elution from the ceramic layers 2 of the ceramic element 1 . More specifically, the cationic elements among the constituent elements of the ceramic element 1 include Zn, Bi, Mn, Co, Sn, Cr, etc. deposited respectively by elution from ZnO, Bi 2 O 3 , MnO, Co 2 O 2 , SnO 2 , Cr 2 O 3 , etc. in the ceramic layers 2 .
  • the surface of the coating film 18 is recessed from the surfaces of wrapping parts 12 a and 12 b of the external electrodes 6 a , 6 b , and the height dimensions of the wrapping parts 12 a , 12 b are larger than the thickness dimension of the coating film 18 .
  • defective mounting such as a tombstone phenomenon is unlikely to be caused.
  • the thickness of the coating film 18 of the varistor 10 A is set to be smaller than the thickness of the coating film 8 of the varistor 10 . This is intended to ensure that the coating film 8 is easily recessed from the wrapping parts 12 a and 12 b of the external electrodes 6 a and 6 b , because the surface of the ceramic element 1 is not provided with any recess 14 in the case of the varistor 10 A.
  • the varistor 10 (with the recesses 14 ) according to an example and a varistor (without any recesses) according to a comparative example were each prepared by the manufacturing method according to the embodiment described previously. However, the immersion of the ceramic element in the etching solution in the step S 7 was skipped in the case of the varistor according to the comparative example.
  • a commercially available latex of a resin component dispersed in an aqueous solvent was used with an etching promoting constituent and a surfactant added thereto, if necessary.
  • an acrylic resin (Trade Name: Nipol LX814A (from Zeon Corporation)) as the resin component was used through the adjustment of the pH to 4.0 with the addition of a sulfuric acid as the etching promoting constituent to the resin.
  • 1 vol % of NEWREX (registered trademark, from NOF Corporation) was added as a surfactant.
  • the resin-containing solution was adjusted so as to have a solid content concentration of 10 wt %.
  • the recesses 14 of the varistor 10 according to the example were formed in such a way that the ceramic element 1 was etched by immersion in a 5% sulfuric acid for 1 minute at room temperature, then washed with pure water, and dried.
  • the recesses 14 are approximately 5 ⁇ m in etching depth.
  • the coating film 8 of the varistor 10 according to the example and the coating film of the varistor according to the comparative example were each formed on the surface of the ceramic element 1 , in such a way that the ceramic element 1 was immersed in the resin-containing solution at room temperature for 10 minutes, washed with pure water, and dried at 150° C. for 30 minutes.
  • the coating films are both approximately 12 ⁇ m in thickness.
  • the wrapping parts 12 a and 12 b of the external electrodes 6 a and 6 b are approximately 10 ⁇ m in height (thickness) dimension. Accordingly, in the case of the varistor 10 (with the recesses 14 ) according to the example, the wrapping parts 12 a and 12 b of the external electrodes 6 a and 6 b are greater in height than the coating film 8 , and the coating film 18 is recessed from the wrapping parts 12 a and 12 b of the external electrodes 6 a and 6 b . On the other hand, in the case of the varistor (without any recesses) according to the comparative example, the wrapping parts of the external electrodes are approximately 2 ⁇ m lower in height than the coating film, and the coating film projects from the wrapping parts of the external electrodes.
  • the prepared varistors according to the example and the comparative example were subjected to the following characterization.
  • the acid resistance was evaluated from the amount of dissolution of the Zn constituent in the case of immersing the varistor in 5 ml of a 0.3% nitric acid solution for 3 minutes at room temperature.
  • the number of samples evaluated is 10.
  • the amount of Zn dissolution was 0.026 mg and smaller in the case of the varistor 10 (with the recesses 14 ) according to the example.
  • the amount of Zn dissolution was 0.525 mg and larger in the case of the varistor (without any recesses) according to the comparative example.
  • the varistor was mounted on a circuit substrate with a solder paste applied thereto to evaluate the tombstone incidence.
  • the number of samples evaluated is 10000.
  • the tombstone incidence was 0% and favorable in the case of the varistor 10 (with the recesses 14 ) according to the example.
  • the tombstone incidence was 0.2% and disadvantageous in the case of the varistor (without any recesses) according to the comparative example.
  • the invention is not to be considered limited to the previously described embodiment, but can be modified variously within the scope of the invention.
  • the ceramic electronic component include, besides varistors, multilayer ceramic capacitors, laminated coils, PTC thermistors, and NTC thermistors.
  • ceramic layers constituting ceramic elements are composed of a ceramic material of Pb(Mg, Nb)O 3 —PbTiO 3 —Pb(Cu, W)—ZnO—MnO 2 as a main constituent mixed with Li 2 O—BaO—B 2 O 3 —SiO 2 as an anti-reducing agent, or a ceramic material containing CaZrO 3 —CaTiO 3 as its main constituent.
  • the cationic elements include Pb, Mg, Nb, Ti, Ba, Li, Zn, Mn, Si, Ca, and Zr each eluted and deposited from Pb(Mg, Nb)O 3 —PbTiO 3 —Pb(Cu, W)—ZnO—MnO 2 , Li 2 O—BaO—B 2 O 3 —SiO 2 , CaZrO 3 —CaTiO 3 , or the like of the ceramic layers.
  • ceramic layers constituting ceramic elements are composed of a magnetic ceramic material such as a Cu—Zn ferrite and a Ni—Zn ferrite. Therefore, among the constituent elements of the ceramic elements, which are contained in the coating films, the cationic elements include Sr, Sn, Fe, Ni, Cu, Zn, Mn, and Co each eluted and deposited from the Cu—Zn ferrite, Ni—Zn ferrite, or the like of the ceramic layers.
  • ceramic layers constituting ceramic elements are composed of, for example, a ceramic material of BaTiO 3 as a main constituent with Y 2 O 2 as a semiconducting agent, SiO 2 and Al 2 O 2 as a curing agent, and MnO 2 as a property improving agent each added thereto and mixed therein. Therefore, among the constituent elements of the ceramic elements, which are contained in the coating films of the PTC thermistors, the cationic elements include Ba, Ti, Y, Si, and Mn each eluted and deposited from BaTiO 2 , Y 2 O 3 , SiO 2 , Al 2 O 2 , or MnO 2 of the ceramic layers.
  • ceramic layers constituting ceramic elements are composed of, for example, a ceramic material of Mn 3 O 4 , NiO, Co 2 O 3 , etc. mixed. Therefore, among the constituent elements of the ceramic elements, which are contained in the coating films of the NTC thermistors, the cationic elements include Mn, Ni, and Co each eluted and deposited from Mn 3 O 4 , NiO, Co 2 O 3 , or the like of the ceramic layers.

Abstract

A ceramic electronic component that includes a ceramic element, and a coating film and external electrodes on a surface of the ceramic element. The coating film includes cationic elements from a constituent element of the ceramic element, which are ionized and deposited from the ceramic element, and a resin. The surface of the coating film is recessed relative to a surface of wrapping parts of the external electrodes on the surface of the ceramic element.

Description

    BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The present invention relates to a ceramic electronic component.
  • 2. Description of the Related Art
  • The ceramics used in electronic components are likely to be chemically eroded by acids or alkalis dues to changes in the ceramic material required by the sophisticated functions of the electronic components.
  • Therefore, as measures against this situation, techniques have been proposed for coating ceramic element surfaces of the electronic components with resin, as described in Japanese Unexamined Patent Application Publication No. 2004-500719 and U.S. Patent Publication No. 2012/0223798.
  • Coating the ceramic element surfaces of the electronic components can reduce the influence of chemical erosion on the ceramic elements, such as that caused by a plating solution during plating or a used in mounting. Further, coating the ceramic element surfaces can, in the case of plating, suppress the growth by plating onto the ceramic element surfaces, and thereby reduce defective conductivity of the electronic component.
  • Furthermore, coating the ceramic element surfaces can prevent ingress of moisture, plating solutions, flux, etc. into the electronic components, and prevent reliability degradation, or electrical property degradation due to deposition by plating onto internal electrodes.
  • SUMMARY OF THE INVENTION
  • However, in the case of coating a ceramic element surface of an electronic component with resin as described in Japanese Unexamined Patent Application Publication No. 2004-500719, film formation is not able to be selectively achieved only on the ceramic element surface, because the resin coating is provided (applied) over the entire surface of the electronic component. Therefore, there is a need for a step of forming a resin coating film over the entire surface of the electronic component before the formation of external electrodes, and removing the resin coating film on end surfaces of the electronic component on which external electrodes are to be formed, and the manufacturing cost is thus increased.
  • In addition, in the case of resin coating carried out after the formation of external electrodes as described in U.S. Patent Publication No. 2012/0223798, a resin coating film is formed only on the ceramic element surface after masking the external electrodes, while the troublesome operation results in high manufacturing cost.
  • Moreover, coating the ceramic element surface of the electronic component with resin increases the size of the electronic component. In particular, in order to completely prevent ingress of plating solutions, etc., the resin coating film needs to have a certain level of thickness, and the surface of the resin coating film may project from the surfaces of wrapping parts of the external electrodes, which are formed on side surfaces of the electronic component.
  • In this case, when the electronic component is mounted on a circuit substrate or the like, there is concern that the occurrence of a tombstone phenomenon will lead to defective mounting.
  • Therefore, an object of the present invention is to provide a ceramic electronic component where a coating film that has favorable chemical erosion resistance can be inexpensively formed, and defective mounting such as a tombstone phenomenon is unlikely to be caused.
  • The present invention provides a ceramic electronic component including a ceramic element, a coating film provided on a surface of the ceramic element, and an external electrode provided on an end of the ceramic element.
  • The coating film includes a resin, and a cationic element among the constituent elements of the ceramic element.
  • The surface of the coating film is recessed from the surface of a wrapping part of the external electrode, which is formed on a side surface of the ceramic element.
  • Among the constituent elements of the ceramic element, the cationic element eluted from the ceramic element is deposited and contained in the coating film. Furthermore, the constituent elements of the ceramic element include at least one of Ba, Ti, Ca, Zr, Fe, Ni, Cu, Zn, Mn, Co, Al, and Si. In addition, a plated film may be provided on the external electrode.
  • In an aspect of the present invention, the coating film includes a resin and at least one kind of cationic elements among the constituent elements of the ceramic element, and the coating film can be selectively formed only on the surface of the ceramic element of the electronic component.
  • In addition, in another aspect of the present invention, the coating film is recessed from the wrapping parts of the external electrodes, and defective mounting such as a tombstone phenomenon is thus unlikely to be caused.
  • In addition, in the ceramic electronic component according another aspect of to the present invention, the wrapping part of the external electrode formed on the side surface of the ceramic element is preferably brought into contact with the surface of the ceramic element. Then, the wrapping parts of the external electrodes are firmly jointed to the surface of the ceramic element.
  • Furthermore, the ceramic electronic component according to a further aspect of the present invention preferably has a coating film provided in recesses formed at the surface of the ceramic element. Then, the thickness of the coating film on the surface of the ceramic element is reduced in appearance just by the depth dimensions of the recesses, and thus, even when the thickness of the coating film is increased in order to enhance the chemical erosion resistance, the surface of the coating film is recessed from the wrapping parts of the external electrodes, and defective mounting such as a tombstone phenomenon is thus unlikely to be caused.
  • In addition, in the ceramic electronic component according to a further aspect of the present invention, the resin preferably has a thermal decomposition temperature of 240° C. or higher. Furthermore, the resin preferably includes at least one of an epoxy resin, a polyimide resin, a silicone resin, a polyamideimide resin, a polyetheretherketone resin, and a fluorine-containing resin. Thus, the ceramic electronic component has high heat resistance.
  • In addition, in the ceramic electronic component according to another aspect of the present invention, the coating film is preferably cross-linked by heating. Thus, the coating film can be formed in a short period of time.
  • According to the various aspects of the present invention, the coating film can be selectively formed only on the surface of the ceramic element, and the ceramic electronic component can be obtained whose manufacturing cost is inexpensive. In addition, the coating film is recessed from the wrapping parts of the external electrodes, and the ceramic electronic component can be thus obtained which is unlikely to cause defective mounting such as a tombstone phenomenon.
  • The foregoing object, and other objects, features, and advantages of the invention will become evident from the following description of embodiments, which will be provided with reference to the drawings.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a cross-sectional view illustrating an embodiment of a ceramic electronic component according to the present invention;
  • FIG. 2 is a flowchart showing an example of a method for manufacturing the ceramic electronic component shown in FIG. 1; and
  • FIG. 3 is a cross-sectional view illustrating a modification example of a ceramic electronic component according to the present invention.
  • DETAILED DESCRIPTION OF THE INVENTION
  • An embodiment of a ceramic electronic component according to the present invention will be described.
  • 1. Ceramic Electronic Component
  • A ceramic electronic component according to the present invention will be described with reference to a varistor as an example.
  • FIG. 1 is a cross-sectional view illustrating a varistor 10 that is a ceramic electronic component according to an aspect of the present invention. The varistor 10 includes a substantially cuboidal ceramic element 1, external electrodes 6 a and 6 b formed on right and left ends of the ceramic element 1, and a coating film 8 formed so as to cover four side surfaces of the ceramic element 1.
  • The ceramic element 1 is a laminated body obtained by stacking a plurality of ceramic layers 2 and multiple pairs of internal electrodes 4 a and 4 b opposed to each other with the ceramic layers 2 interposed therebetween.
  • The ceramic layers 2 are composed of a ceramic material in which Bi2O3 is present as a second phase at grain boundaries of a sintered body of ZnO crystal grains with Mn, Co, Sn, or Cr therein as a solid solution.
  • The internal electrodes 4 a have ends extended to the left end surface of the ceramic body 1, and electrically connected to the external electrode 6 a. The internal electrodes 4 b have ends extended to the right end surface of the ceramic body 1, and electrically connected to the external electrode 6 b. Thus, a varistor function is achieved at sites with the internal electrodes 4 a and 4 b opposed. The internal electrodes 4 a and 4 b are composed of Ag, Cu, Ni, Pd, or an alloy of these metals.
  • The external electrodes 6 a and 6 b respectively have wrapping parts 12 a and 12 b formed to extend on the four side surfaces of the ceramic element 1. The wrapping parts 12 a and 12 b are formed directly on the surface of the ceramic element 1. Thus, the wrapping parts 12 a and 12 b are firmly joined to the surface of the ceramic element 1.
  • Plated films 7 a and 7 b are formed on the surfaces of the external electrodes 6 a and 6 b. The plated films 7 a and 7 b protect the external electrodes 6 a and 6 b, and make solderability of the external electrodes 6 a and 6 b favorable.
  • On parts of the surface of the ceramic element 1 other than regions on which the external electrodes 6 a and 6 b are formed, a coating film 8 is formed. The coating film 8 is provided in recesses 14 formed by etching the surface of the ceramic element 1 excluding the regions for the external electrodes 6 a and 6 b. Thus, the coating film 8 provided in contact with the surfaces of the recesses 14 roughened by etching is firmly joined to the surfaces of the recesses 14 due to the anchor effect.
  • The coating film 8 includes a resin, and cationic elements among the constituent elements of the ceramic element 1. The cationic elements among the constituent elements of the ceramic element 1, which are contained in the coating film 8, are deposited by partial elution from the ceramic layers 2 of the ceramic element 1. More specifically, the cationic elements among the constituent elements of the ceramic element 1 include Zn, Bi, Mn, Co, Sn, Cr, etc. deposited respectively by elution from ZnO, Bi2O3, MnO, Co2O2, SnO2, Cr2O3, etc. in the ceramic layers 2.
  • The resin included in the coating film 8 is a polyvinylidene chloride resin, an acrylic resin, an epoxy resin, a polyimide resin, a silicone resin, a polyamideimide resin, a polyetheretherketone resin, a fluorine-containing resin, or the like. The varistor 10 typically undergoes a mounting step with soldering, and the coating film 8 preferably has high heat resistance (240° C. or higher). Accordingly, a resin is preferred which has a thermal decomposition temperature of 240° C. or higher. In this regard, there is a relationship of: (polyvinylidene chloride resin, acrylic resin)<epoxy resin<(polyimide resin, polyamideimide resin, polyetheretherketone resin, silicone resin, fluorine-containing resin) in terms of heat resistance.
  • In the case of the thus configured varistor 10, the coating film 8 includes a resin and cationic elements among the constituent elements of the ceramic element 1, and the coating film 8 can be selectively formed only on the surface of the ceramic element of the varistor 10. Accordingly, the varistor 10 can be obtained whose manufacturing cost is inexpensive.
  • Furthermore, the thickness of the coating film 8 on the surface of the ceramic element 1 is reduced in appearance just by the depth dimensions of the recesses 14, and thus, even when the thickness of the coating film 8 is increased in order to enhance the chemical erosion resistance, the surface of the coating film 8 can be recessed from the surfaces of the wrapping parts 12 a and 12 b of the external electrodes 6 a and 6 b, and defective mounting such as a tombstone phenomenon is thus unlikely to be caused.
  • 2. Method for Manufacturing Ceramic Electronic Component
  • Next, an example of a method for manufacturing the varistor 10 will be described with reference to FIG. 2. FIG. 2 is a flowchart showing an example of a method for manufacturing the varistor 10.
  • In a step S1, an organic binder, a dispersant, a plasticizer, etc. are added to a ceramic material in which Bi2O3 is present as a second phase at grain boundaries of a sintered body of ZnO crystal grains with Mn, Co, Sn, or Cr therein as a solid solution, thereby preparing slurry for sheet forming.
  • Next, in a step S2, the slurry for sheet forming is formed into sheets by a doctor blade method to provide rectangular ceramic green sheets.
  • Next, in a step S3, an internal electrode paste containing Ag is applied onto the ceramic green sheets by a screen printing method to form electrode paste films which are to be the internal electrodes 4 a and 4 b.
  • Next, in a step S4, the multiple ceramic green sheets with the electrode paste films formed are stacked so as to alternate directions in which ends of the electrode paste films are extended, and subjected to pressure bonding. This laminated ceramic green sheet is cut into a size for individual ceramic elements 1 to provide a plurality of unfired ceramic elements 1.
  • Next, in a step S5, the unfired ceramic elements 1 are subjected to binder removal treatment at a temperature of 400° C. to 500° C. Thereafter, the unfired ceramic elements 1 are subjected to firing for 2 hours at a temperature of 900° C. to 1000° C. to provide sintered ceramic elements 1. The ceramic green sheets and the electrode paste films are subjected to co-firing, and the ceramic green sheets serve as the ceramic layers 2, whereas the electrode paste films serve as the internal electrodes 4 a and 4 b.
  • Next, in a step S6, an external electrode paste (AgPd alloy paste) is applied to both ends of the sintered ceramic elements 1. Thereafter, on the sintered ceramic elements 1, the external electrode paste is heated at a temperature of 900° C. to form the external electrodes 6 a and 6 b electrically connected respectively to the internal electrodes 4 a and 4 b.
  • Next, in a step S7, the ceramic elements 1 are immersed in an etching solution to etch the surfaces of the ceramic elements 1 excluding the regions for the external electrodes 6 a and 6 b, thereby forming the recesses 14. Used for the etching solution is a solution that dissolves the ceramic elements 1, but does not dissolve the external electrodes 6 a and 6 b. Specifically, a solution is used which contains an inorganic acid such as a sulfuric acid, a hydrochloric acid, a hydrofluoric acid, and a phosphoric acid.
  • Next, in a step S8, to the ceramic elements 1, a resin-containing solution is provided by an immersion method, or applied by spin coating. The resin-containing solution has the function of finely etching the surfaces of the ceramic elements 1 to ionize the constituent elements of the ceramic elements 1, and includes a resin component dissolved or dispersed in an aqueous solvent. Furthermore, the resin-containing solution includes a neutralizer for dissolution or dispersion of the resin component, and if necessary, a surfactant for reaction with cationic elements among the dissolved constituent elements of the ceramic elements. It is to be noted that after providing the resin-containing solution, the ceramic elements 1 are washed with a polar solvent such as pure water, if necessary.
  • Therefore, the resin-containing solution finely etches (dissolves) the surfaces of the ceramic elements 1 to ionize the constituent elements of the ceramic elements 1. In regard to the etching (dissolving) function of the resin-containing solution, the etching (dissolving) reaction can be developed just with the constituents of the resin-containing solution without adding any etching promoting constituent such as halogen, because the main constituent is ZnO in the case of the varistor 10. More specifically, the etching (dissolving) reaction proceeds when the pH of the resin-containing solution is set in a pH range (pH<5, pH>11) in which Zn is present stably as ions.
  • Then, the resin component dissolved (dispersed) in the resin-containing solution reacts with cationic elements among the ionized constituent elements of the ceramic elements 1 to neutralize the charge of the resin component. As a result, the resin component settles out along with cationic elements among the constituent elements of the ceramic elements 1, and selectively deposits only on the surface of the ceramic element. Accordingly, in the deposited resin component, at least one kind of cationic elements, which are defined as ionized constituent elements of the ceramic elements, are incorporated.
  • On the other hand, the resin component is not deposited on the external electrodes 6 a and 6 b. However, at the interfaces between the ceramic elements 1 and the external electrodes 6 a and 6 b, the resin component may slightly extend on the surfaces of the external electrodes 6 a and 6 b. This is believed to be the resin component deposited on the surface of the ceramic element, which slightly extends to the external electrodes 6 a and 6 b, rather than the deposition reaction proceeding at the surfaces of the external electrodes 6 a and 6 b.
  • The resin included in the resin-containing solution is a polyvinylidene chloride resin, an acrylic resin, an epoxy resin, a polyimide resin, a silicone resin, a polyamideimide resin, a polyetheretherketone resin, a fluorine-containing resin, or the like, but basically, it does not matter what kind as long as the resin is deposited by the present treatment.
  • In this way, the coating film 8 including the cationic elements among the constituent elements of the ceramic elements 1, which are ionized and deposited from the ceramic elements 1, and the resin is formed on the surface of the ceramic element. Thereafter, the coating film 8 is subjected to heating treatment. The heating treatment is intended to accelerate a cross-linking reaction between the resin components in the resin-containing solution deposited, and the heating condition varies depending on the type of the resin component. In general, the cross-linking reaction is likely to proceed under high temperature. However, the excessively increased temperature increases the decomposition reaction of the resin component. Accordingly, it is preferable to set optimum temperature and time in accordance with the resin component.
  • Next, in a step S9, the plated films 7 a and 7 b are formed on the external electrodes 6 a and 6 b by an electrolytic or electroless plating method. The plated films 7 a and 7 b adopt, for example, a double structure composed of a Ni plated film as a lower layer and an Sn plated film as an upper layer.
  • In this way, the coating film 8 can be selectively formed only on the surface of the ceramic element. Accordingly, the varistor 10 whose manufacturing cost is inexpensive can be manufactured with favorable mass productivity. In addition, the method can be also adapted to the varistor 10 including the external electrodes 6 a and 6 b which have a complex shape or microstructure, because the coating film 8 is formed by chemical action.
  • 3. Modification Example of Ceramic Electronic Component
  • FIG. 3 is a cross-sectional view illustrating a modification example of the varistor 10.
  • Except that the surface of a ceramic element 1 has no recess 14 formed, a varistor 10A has the same structure as the varistor 10 shown in FIG. 1, and detailed description thereof will be thus omitted.
  • In the case of the varistor 10A, on the surface of the ceramic element 1 excluding the regions for external electrodes 6 a and 6 b, a coating film 18 is formed. The coating film 18 including a resin, and cationic elements among the constituent elements of the ceramic element 1 is selectively formed only on the surface of the ceramic element 1 of the varistor 10A.
  • The coating film 18 includes a resin, and cationic elements among the constituent elements of the ceramic element 1. The cationic elements among the constituent elements of the ceramic element 1, which are contained in the coating film 18, are deposited by partial elution from the ceramic layers 2 of the ceramic element 1. More specifically, the cationic elements among the constituent elements of the ceramic element 1 include Zn, Bi, Mn, Co, Sn, Cr, etc. deposited respectively by elution from ZnO, Bi2O3, MnO, Co2O2, SnO2, Cr2O3, etc. in the ceramic layers 2.
  • Furthermore, the surface of the coating film 18 is recessed from the surfaces of wrapping parts 12 a and 12 b of the external electrodes 6 a, 6 b, and the height dimensions of the wrapping parts 12 a, 12 b are larger than the thickness dimension of the coating film 18. Thus, defective mounting such as a tombstone phenomenon is unlikely to be caused.
  • It is to be noted that the thickness of the coating film 18 of the varistor 10A is set to be smaller than the thickness of the coating film 8 of the varistor 10. This is intended to ensure that the coating film 8 is easily recessed from the wrapping parts 12 a and 12 b of the external electrodes 6 a and 6 b, because the surface of the ceramic element 1 is not provided with any recess 14 in the case of the varistor 10A.
  • EXAMPLE 1. Preparation of Example and Comparative Example
  • The varistor 10 (with the recesses 14) according to an example and a varistor (without any recesses) according to a comparative example were each prepared by the manufacturing method according to the embodiment described previously. However, the immersion of the ceramic element in the etching solution in the step S7 was skipped in the case of the varistor according to the comparative example.
  • As the resin-containing solution, a commercially available latex of a resin component dispersed in an aqueous solvent was used with an etching promoting constituent and a surfactant added thereto, if necessary.
  • As the resin-containing solution, an acrylic resin (Trade Name: Nipol LX814A (from Zeon Corporation)) as the resin component was used through the adjustment of the pH to 4.0 with the addition of a sulfuric acid as the etching promoting constituent to the resin. To this resin, 1 vol % of NEWREX (registered trademark, from NOF Corporation) was added as a surfactant. The resin-containing solution was adjusted so as to have a solid content concentration of 10 wt %.
  • The recesses 14 of the varistor 10 according to the example were formed in such a way that the ceramic element 1 was etched by immersion in a 5% sulfuric acid for 1 minute at room temperature, then washed with pure water, and dried. The recesses 14 are approximately 5 μm in etching depth.
  • The coating film 8 of the varistor 10 according to the example and the coating film of the varistor according to the comparative example were each formed on the surface of the ceramic element 1, in such a way that the ceramic element 1 was immersed in the resin-containing solution at room temperature for 10 minutes, washed with pure water, and dried at 150° C. for 30 minutes. The coating films are both approximately 12 μm in thickness.
  • The wrapping parts 12 a and 12 b of the external electrodes 6 a and 6 b are approximately 10 μm in height (thickness) dimension. Accordingly, in the case of the varistor 10 (with the recesses 14) according to the example, the wrapping parts 12 a and 12 b of the external electrodes 6 a and 6 b are greater in height than the coating film 8, and the coating film 18 is recessed from the wrapping parts 12 a and 12 b of the external electrodes 6 a and 6 b. On the other hand, in the case of the varistor (without any recesses) according to the comparative example, the wrapping parts of the external electrodes are approximately 2 μm lower in height than the coating film, and the coating film projects from the wrapping parts of the external electrodes.
  • 2. Characterization Methods and Evaluation Results in Example and Comparative Example
  • The prepared varistors according to the example and the comparative example were subjected to the following characterization.
  • (a) Solubility in Acid
  • With the use of ICP-AES, the acid resistance was evaluated from the amount of dissolution of the Zn constituent in the case of immersing the varistor in 5 ml of a 0.3% nitric acid solution for 3 minutes at room temperature. The number of samples evaluated is 10.
  • As a result, the amount of Zn dissolution was 0.026 mg and smaller in the case of the varistor 10 (with the recesses 14) according to the example. On the other hand, the amount of Zn dissolution was 0.525 mg and larger in the case of the varistor (without any recesses) according to the comparative example.
  • (b) Mountability
  • The varistor was mounted on a circuit substrate with a solder paste applied thereto to evaluate the tombstone incidence. The number of samples evaluated is 10000. As a result, the tombstone incidence was 0% and favorable in the case of the varistor 10 (with the recesses 14) according to the example. On the other hand, the tombstone incidence was 0.2% and disadvantageous in the case of the varistor (without any recesses) according to the comparative example.
  • It is to be noted that the invention is not to be considered limited to the previously described embodiment, but can be modified variously within the scope of the invention. Examples of the ceramic electronic component include, besides varistors, multilayer ceramic capacitors, laminated coils, PTC thermistors, and NTC thermistors.
  • In the case of multilayer ceramic capacitors, ceramic layers constituting ceramic elements are composed of a ceramic material of Pb(Mg, Nb)O3—PbTiO3—Pb(Cu, W)—ZnO—MnO2 as a main constituent mixed with Li2O—BaO—B2O3—SiO2 as an anti-reducing agent, or a ceramic material containing CaZrO3—CaTiO3 as its main constituent. Therefore, among the constituent elements of the ceramic elements, which are contained in the coating films, the cationic elements include Pb, Mg, Nb, Ti, Ba, Li, Zn, Mn, Si, Ca, and Zr each eluted and deposited from Pb(Mg, Nb)O3—PbTiO3—Pb(Cu, W)—ZnO—MnO2, Li2O—BaO—B2O3—SiO2, CaZrO3—CaTiO3, or the like of the ceramic layers.
  • In the case of laminated coils, ceramic layers constituting ceramic elements are composed of a magnetic ceramic material such as a Cu—Zn ferrite and a Ni—Zn ferrite. Therefore, among the constituent elements of the ceramic elements, which are contained in the coating films, the cationic elements include Sr, Sn, Fe, Ni, Cu, Zn, Mn, and Co each eluted and deposited from the Cu—Zn ferrite, Ni—Zn ferrite, or the like of the ceramic layers.
  • In the case of PTC thermistors, ceramic layers constituting ceramic elements are composed of, for example, a ceramic material of BaTiO3 as a main constituent with Y2O2 as a semiconducting agent, SiO2 and Al2O2 as a curing agent, and MnO2 as a property improving agent each added thereto and mixed therein. Therefore, among the constituent elements of the ceramic elements, which are contained in the coating films of the PTC thermistors, the cationic elements include Ba, Ti, Y, Si, and Mn each eluted and deposited from BaTiO2, Y2O3, SiO2, Al2O2, or MnO2 of the ceramic layers.
  • In the case of NTC thermistors, ceramic layers constituting ceramic elements are composed of, for example, a ceramic material of Mn3O4, NiO, Co2O3, etc. mixed. Therefore, among the constituent elements of the ceramic elements, which are contained in the coating films of the NTC thermistors, the cationic elements include Mn, Ni, and Co each eluted and deposited from Mn3O4, NiO, Co2O3, or the like of the ceramic layers.

Claims (14)

What is claimed is:
1. A ceramic electronic component comprising:
a ceramic element;
a coating film on a surface of the ceramic element; and
an external electrode on an end of the ceramic element,
wherein the coating film includes a resin, and a cationic element that is a constituent element of the ceramic element, and
a surface of the coating film is recessed relative to a surface of a wrapping part of the external electrode, the wrapping part being located on the surface of the ceramic element.
2. The ceramic electronic component according to claim 1, wherein the wrapping part of the external electrode is in direct contact with the surface of the ceramic element.
3. The ceramic electronic component according to claim 1, wherein the surface of the ceramic element includes a recess and the coating film is provided in the recess.
4. The ceramic electronic component according to claim 3, wherein the wrapping part of the external electrode is not in the recess.
5. The ceramic electronic component according to claim 3, wherein the recess is on a side surface of the ceramic element.
6. The ceramic electronic component according to claim 3, wherein the recess is on four side surfaces of the ceramic element, the surface being one of the four side surfaces.
7. The ceramic electronic component according to claim 1, wherein the surface is a side surface of the ceramic element.
8. The ceramic electronic component according to claim 1, wherein the coating film is on four side surfaces of the ceramic element, the surface being one of the four side surfaces.
9. The ceramic electronic component according to claim 1, wherein constituent element of the ceramic element includes at least one of Ba, Ti, Ca, Zr, Fe, Ni, Cu, Zn, Mn, Co, Al, and Si.
10. The ceramic electronic component according to claim 1, wherein the resin has a thermal decomposition temperature of 240° C. or higher.
11. The ceramic electronic component according to claim 1, wherein the resin comprises at least one of an epoxy resin, a polyimide resin, a silicone resin, a polyamideimide resin, a polyetheretherketone resin, and a fluorine-containing resin.
12. The ceramic electronic component according to claim 1, wherein the coating film contains cross-linked resin components.
13. The ceramic electronic component according to claim 1, further comprising a plated film on the external electrode.
14. The ceramic electronic component according to claim 1, wherein a thickness of the coating film is smaller than a thickness of the wrapping part of the external electrode.
US14/805,546 2014-07-28 2015-07-22 Ceramic electronic component Active US9959975B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014153086A JP6274044B2 (en) 2014-07-28 2014-07-28 Ceramic electronic components
JP2014-153086 2014-07-28

Publications (2)

Publication Number Publication Date
US20160027561A1 true US20160027561A1 (en) 2016-01-28
US9959975B2 US9959975B2 (en) 2018-05-01

Family

ID=55167263

Family Applications (1)

Application Number Title Priority Date Filing Date
US14/805,546 Active US9959975B2 (en) 2014-07-28 2015-07-22 Ceramic electronic component

Country Status (4)

Country Link
US (1) US9959975B2 (en)
JP (1) JP6274044B2 (en)
KR (2) KR101996356B1 (en)
CN (1) CN105304322B (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10181369B2 (en) * 2015-03-04 2019-01-15 Murata Manufacturing Co., Ltd. NTC thermistor to be embedded in a substrate, and method for producing the same
US10446355B2 (en) * 2017-04-27 2019-10-15 Littelfuse, Inc. Hybrid device structures including negative temperature coefficient/positive temperature coefficient device
US10529492B1 (en) * 2018-09-06 2020-01-07 Samsung Electro-Mechanics Co., Ltd. Ceramic electronic component
CN111105931A (en) * 2018-10-29 2020-05-05 三星电机株式会社 Capacitor assembly
US10903011B2 (en) 2017-09-29 2021-01-26 Samsung Electro-Mechanics Co., Ltd. Multilayer electronic component and method of manufacturing the same
US20210090812A1 (en) * 2018-10-17 2021-03-25 Samsung Electro-Mechanics Co., Ltd. Multilayer ceramic electronic component and method of manufacturing the same
US20220208464A1 (en) * 2020-12-31 2022-06-30 Samsung Electro-Mechanics Co., Ltd. Multilayer ceramic electronic component
US11380485B2 (en) * 2019-07-17 2022-07-05 Murata Manufacturing Co., Ltd. Electronic component
CN115083774A (en) * 2021-03-16 2022-09-20 株式会社村田制作所 Multilayer ceramic capacitor
US11688559B2 (en) * 2019-03-28 2023-06-27 Taiyo Yuden Co., Ltd. Multilayer ceramic capacitor having external electrodes provided with fluorine compound

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102059440B1 (en) * 2017-09-29 2019-12-27 삼성전기주식회사 Method of preparaing multalayered electronic component
WO2020018651A1 (en) 2018-07-18 2020-01-23 Avx Corporation Varistor passivation layer and method of making the same
KR102575046B1 (en) 2020-09-04 2023-09-06 한국전자기술연구원 Ceramic transducer electronic component and method for formating electrode thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5275707A (en) * 1989-10-30 1994-01-04 Shinto Paint Co., Ltd. Electrodeposition coating composition and method
US5614074A (en) * 1994-12-09 1997-03-25 Harris Corporation Zinc phosphate coating for varistor and method
US6214685B1 (en) * 1998-07-02 2001-04-10 Littelfuse, Inc. Phosphate coating for varistor and method
US6232867B1 (en) * 1999-08-27 2001-05-15 Murata Manufacturing Co., Ltd. Method of fabricating monolithic varistor
US6535105B2 (en) * 2000-03-30 2003-03-18 Avx Corporation Electronic device and process of making electronic device
US20040169267A1 (en) * 2002-10-29 2004-09-02 Tdk Corporation Chip shaped electronic device and a method of producing the same
US6841191B2 (en) * 2002-02-08 2005-01-11 Thinking Electronic Industrial Co., Ltd. Varistor and fabricating method of zinc phosphate insulation for the same
US7659806B2 (en) * 2007-03-02 2010-02-09 Rohm Co., Ltd. Chip resistor and method of making the same
US8009012B2 (en) * 2007-07-24 2011-08-30 Tdk Corporation Stacked electronic part and method of manufacturing the same

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0917607A (en) * 1995-06-26 1997-01-17 Taiyo Yuden Co Ltd Chip type circuit component and its manufacture
JPH09205005A (en) 1996-01-24 1997-08-05 Matsushita Electric Ind Co Ltd Electronic component and manufacture thereof
JP2001093770A (en) * 1999-09-24 2001-04-06 Matsushita Electric Ind Co Ltd Surface mount electronic component
JP2010123865A (en) * 2008-11-21 2010-06-03 Murata Mfg Co Ltd Ceramic electronic component and component built-in substrate
JP5440309B2 (en) * 2010-03-24 2014-03-12 株式会社村田製作所 Manufacturing method of multilayer ceramic electronic component
JP5522533B2 (en) * 2010-05-27 2014-06-18 三菱マテリアル株式会社 Surface-mount type electronic component and manufacturing method
US8584348B2 (en) 2011-03-05 2013-11-19 Weis Innovations Method of making a surface coated electronic ceramic component
KR101376921B1 (en) * 2012-12-11 2014-03-20 삼성전기주식회사 Multilayer ceramic capacitor and method of manufacturing the same
KR101721630B1 (en) * 2013-01-29 2017-03-30 가부시키가이샤 무라타 세이사쿠쇼 Ceramic electronic component and manufacturing method therefor

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5275707A (en) * 1989-10-30 1994-01-04 Shinto Paint Co., Ltd. Electrodeposition coating composition and method
US5614074A (en) * 1994-12-09 1997-03-25 Harris Corporation Zinc phosphate coating for varistor and method
US6214685B1 (en) * 1998-07-02 2001-04-10 Littelfuse, Inc. Phosphate coating for varistor and method
US6232867B1 (en) * 1999-08-27 2001-05-15 Murata Manufacturing Co., Ltd. Method of fabricating monolithic varistor
US6535105B2 (en) * 2000-03-30 2003-03-18 Avx Corporation Electronic device and process of making electronic device
US6841191B2 (en) * 2002-02-08 2005-01-11 Thinking Electronic Industrial Co., Ltd. Varistor and fabricating method of zinc phosphate insulation for the same
US20040169267A1 (en) * 2002-10-29 2004-09-02 Tdk Corporation Chip shaped electronic device and a method of producing the same
US7659806B2 (en) * 2007-03-02 2010-02-09 Rohm Co., Ltd. Chip resistor and method of making the same
US8009012B2 (en) * 2007-07-24 2011-08-30 Tdk Corporation Stacked electronic part and method of manufacturing the same

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10181369B2 (en) * 2015-03-04 2019-01-15 Murata Manufacturing Co., Ltd. NTC thermistor to be embedded in a substrate, and method for producing the same
US10446355B2 (en) * 2017-04-27 2019-10-15 Littelfuse, Inc. Hybrid device structures including negative temperature coefficient/positive temperature coefficient device
US10903011B2 (en) 2017-09-29 2021-01-26 Samsung Electro-Mechanics Co., Ltd. Multilayer electronic component and method of manufacturing the same
US10529492B1 (en) * 2018-09-06 2020-01-07 Samsung Electro-Mechanics Co., Ltd. Ceramic electronic component
US10535469B1 (en) * 2018-09-06 2020-01-14 Samsung Electro-Mechanics Co., Ltd. Ceramic electronic component
US10886068B2 (en) 2018-09-06 2021-01-05 Samsung Electro-Mechanics Co., Ltd. Ceramic electronic component
US11211202B2 (en) 2018-10-17 2021-12-28 Samsung Electro-Mechanics Co., Ltd. Multilayer ceramic electronic component and method of manufacturing the same
US11551874B2 (en) * 2018-10-17 2023-01-10 Samsung Electro-Mechanics Co., Ltd. Multilayer ceramic electronic component and method of manufacturing the same
US20210090812A1 (en) * 2018-10-17 2021-03-25 Samsung Electro-Mechanics Co., Ltd. Multilayer ceramic electronic component and method of manufacturing the same
CN111105931A (en) * 2018-10-29 2020-05-05 三星电机株式会社 Capacitor assembly
US11152155B2 (en) 2018-10-29 2021-10-19 Samsung Electro-Mechanics Co., Ltd. Capacitor component having secondary phase material contained in external electrode thereof
US10804034B2 (en) * 2018-10-29 2020-10-13 Samsung Electro-Mechanics Co., Ltd. Capacitor component having secondary phase material contained in external electrode thereof
US11688559B2 (en) * 2019-03-28 2023-06-27 Taiyo Yuden Co., Ltd. Multilayer ceramic capacitor having external electrodes provided with fluorine compound
US11380485B2 (en) * 2019-07-17 2022-07-05 Murata Manufacturing Co., Ltd. Electronic component
US20220208464A1 (en) * 2020-12-31 2022-06-30 Samsung Electro-Mechanics Co., Ltd. Multilayer ceramic electronic component
US11901131B2 (en) * 2020-12-31 2024-02-13 Samsung Electro-Mechanics Co., Ltd. Multilayer ceramic electronic component including external electrodes having improved reliability
CN115083774A (en) * 2021-03-16 2022-09-20 株式会社村田制作所 Multilayer ceramic capacitor

Also Published As

Publication number Publication date
JP6274044B2 (en) 2018-02-07
JP2016031989A (en) 2016-03-07
US9959975B2 (en) 2018-05-01
CN105304322B (en) 2019-03-01
KR20170127398A (en) 2017-11-21
KR101996356B1 (en) 2019-10-01
KR20160013815A (en) 2016-02-05
CN105304322A (en) 2016-02-03

Similar Documents

Publication Publication Date Title
US9959975B2 (en) Ceramic electronic component
US9997293B2 (en) Ceramic electronic component and manufacturing method therefor
US10304630B2 (en) Ceramic electronic component and manufacturing method therefor
US11328851B2 (en) Ceramic electronic component and manufacturing method therefor
US9595391B2 (en) Ceramic electronic component and manufacturing method therefor
JP5910533B2 (en) Electronic component, electronic component-embedded substrate, and electronic component manufacturing method
JP7131897B2 (en) Ceramic electronic component and manufacturing method thereof
KR100498682B1 (en) Chip electronic component
CN109786106B (en) Ceramic electronic device and method for manufacturing ceramic electronic device
JP2006229178A (en) Semiconductive chip element having insulating coating layer and method of manufacturing same
JP2004152824A (en) Chip electronic part and its manufacturing method
JP4515334B2 (en) Barrel plating method and electronic component manufacturing method
JP6119513B2 (en) Electronic components
JP2003272906A (en) Ceramic element and manufacturing method of the same
JP2012216699A (en) Chip ptc thermistor
KR20140128914A (en) Manufacturing of Multi-layered ceramic electronic parts

Legal Events

Date Code Title Description
AS Assignment

Owner name: MURATA MANUFACTURING CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:INOUE, MITSUNORI;OKUTOMI, YOSHIHITO;MORI, TOMOHIKO;REEL/FRAME:036149/0864

Effective date: 20150629

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4